Objectives of this research were to evaluate functions and structures of starches from exotic × adapted inbred lines and exotic lines, to confirm that the functional traits continue into the next generation of inbreeding, and to establish relationships between the fine structure and functional properties of the starches. Several lines were characterized from the successive generations of exotic crosses and exotic inbreds containing kernels with unusual, and potentially useful, thermal properties as measured by differential scanning calorimetry (DSC, gelatinization onset temperature <60 °C or range of gelatinization temperature >14 °C). The frequency of these traits increased with succeeding generations, when selection of the plants was based on the desired trait. Strong correlations were found between DSC and Rapid ViscoAnalyser properties and the granular structure (granular size distribution and branch-chain-length distribution of amylopectin).